US7344590B2 - Silver pigments - Google Patents

Silver pigments Download PDF

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US7344590B2
US7344590B2 US10/811,143 US81114304A US7344590B2 US 7344590 B2 US7344590 B2 US 7344590B2 US 81114304 A US81114304 A US 81114304A US 7344590 B2 US7344590 B2 US 7344590B2
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pigment
silver
platelet
coating
pigments
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Christoph Schmidt
Tanja Delp
Johann Dietz
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1062—Interference pigments characterized by the core material the core consisting of an organic compound, e.g. Liquid Crystal Polymers [LCP], Polymers or natural pearl essence
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/302—Thickness of a layer with high refractive material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

  • the present invention relates to silver interference pigments based on platelet-shaped, transparent, low-refractive-index substrates and to the use thereof in paints, coatings, printing inks, plastics, as dopants for the laser marking of plastics and papers, as additives in the foods and pharmaceuticals sectors and in cosmetic formulations.
  • Luster or effect pigments are employed in many areas of industry, in particular in the area of automotive finishes, decorative coatings, plastics, paints, printing inks and in cosmetic formulations.
  • Luster pigments which exhibit an angle-dependent color change between a plurality of interference colors, are of particular interest for automotive finishes and in forgery-proof documents of value.
  • Pearlescent pigments are of particular importance. Pearlescent pigments are prepared by coating an inorganic, platelet-shaped support with a high-refractive-index, usually oxidic layer. The color of these pigments is caused by wavelength-selective partial reflection and interference of the reflected or transmitted light at the medium/oxide or oxide/substrate interfaces.
  • the interference color of these pigments is determined by the thickness of the oxide layer.
  • the hue of a silver pigment is generated by a (in the optical sense) single high-refractive-index layer whose optical thickness causes a reflection maximum (1st order) in the visible wavelength range at about 500 nm. This wavelength is perceived by the human eye as the color green. However, the intensity curve of this maximum on its wavelength axis is so broad that so much light is reflected throughout the region of visible light that the human eye perceives a very bright, but colorless impression.
  • the intensity of the reflected light in an arrangement of a plurality of layers with alternating high and low refractive indexes increases greatly compared with a single layer.
  • the application of a TiO 2 —SiO 2 —TiO 2 layer system to mica particles increases the intensity of the reflected light by about 60% compared with a TiO 2 single-layer system.
  • the profile of the light reflected by interference is significantly more pronounced, so that an intense and bright reflection color must be expected for a multilayered system of this type. Pigments of this type are described in DE 196 18 569 A1.
  • the prior art discloses silver pigments based on mica platelets which have a very broad scattering of the layer thickness and therefore have a neutral behavior with respect to the interference color.
  • Pearlescent pigments that have a single high-refractive-index coating of mica therefore represent single-layer optical systems, i.e. the interference color is determined exclusively by the layer thickness of the high-refractive-index metal-oxide layer.
  • the coloristic design latitude of a mica/metal oxide silver pigment is therefore very restricted.
  • mica particles owing to their layer structure, have irregularities on the surface which cause scattering and thus reduce the transparency and coloristic quality of the product. Furthermore, mica exhibits a more or less highly pronounced grey-brown body color. This property reduces the transparency further and influences the absorption color of the application media in an undesired manner.
  • multilayered pigments which cause a silver color impression, as described, for example, in EP 1213330 A1 are known.
  • an intense color can be suppressed by the SiO 2 layer of the TiO 2 —SiO 2 —TiO 2 layer sequence having been applied very thinly (about 50 nm).
  • These pigments like the single-layered mica-based silver pigments, offer only a very small latitude in the design of the coloristic properties and have the above-mentioned disadvantages of mica as substrate.
  • the object of the present invention is therefore to provide a silver-colored interference pigment which is distinguished, in particular, by high transparency, a pure-white body color and coloristic design possibilities which go beyond an exclusively silver effect.
  • a specific transparent, low-refractive-index platelet such as, for example, an SiO 2 platelet
  • a thin TiO 2 layer causes a silver color impression. This is achieved through the coating of the platelet with a TiO 2 layer whose thickness is “matched” precisely to the thickness of the platelet.
  • the interference color of a thin layer is determined by its thickness.
  • the color is a result of the reflection of the whole stack of layers as one reflection system.
  • the pigments according to the invention exhibit the following properties:
  • the pigments according to the invention are distinguished over the known interference pigments by the following features:
  • the said hue can be varied over a broad range by adjusting (i.e., “matching”) the TiO 2 layer thickness and through the choice of transparent platelets, such as, for example, SiO 2 platelets, of various thickness without losing the impression of an interference pigment.
  • matching is conventional.
  • the invention therefore relates to silver interference pigments based on platelet-shaped, transparent, low-refractive-index substrates which have a high-refractive-index coating consisting of TiO 2 having a layer thickness of 5-300 nm and optionally an outer protective layer.
  • the invention furthermore relates to the use of the silver pigments according to the invention in paints, coatings, printing inks, plastics, button pastes, ceramic materials, glasses, for seed coating, as dopants in the laser marking of plastics and papers, as additives for coloring in the foods and pharmaceuticals sectors and in particular in cosmetic formulations.
  • the pigments according to the invention are furthermore also suitable for the preparation of pigment compositions and for the preparation of dry preparations, such as, for example, granules, chips, pellets, briquettes, etc.
  • the dry preparations are particularly suitable for printing inks and for cosmetic formulations.
  • Suitable substrates are all low refractive index inorganic and organic transparent materials which can be produced in the form of finely divided platelets having a narrow thickness distribution.
  • Suitable organic substrates are, inter alia, polymers, such as, for example, polyesters (for example PET), polycarbonates, polyimides and polymethacrylates.
  • Suitable base substrates for the interference pigments according to the invention are substrates having a refractive index of ⁇ 1.9, for example platelet-shaped SiO 2 platelets, as described, for example, in WO 93/08237. Furthermore, besides the said SiO 2 platelets, any platelet-shaped, transparent substrate known to the person skilled in the art, such as, for example, Al 2 O 3 platelets, glass platelets and platelet-shaped plastic particles, is suitable. Very particularly preferred substrates are SiO 2 platelets. The particular properties, such as the tuneable hue and in particular the angle dependence thereof, are particularly supported by a defined average density with a narrow thickness distribution.
  • interference pigments based on substrates of SiO 2 , Al 2 O 3 , all single crystals with a flaky appearance and glass platelets, all coated with a thin titanium dioxide layer.
  • the standard deviation of the thickness of the substrate platelets is therefore ⁇ 20%, more preferably ⁇ 10% and particularly preferably ⁇ 5%, based on the average layer thickness thereof.
  • Low refractive index is understood in the art to refer to materials with refractive index ⁇ 1.9, while “high” refractive index refers to >1.9.
  • the size of the base substrate is not crucial per se and can be matched to the particular application.
  • the platelet-shaped transparent substrates have an average thickness of between 0.02 and 10 ⁇ m, preferably between 0.03 and 5 ⁇ m, in particular between 0.05 and 3 ⁇ m.
  • the size in the two other dimensions is usually between 1 and 450 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 5 and 100 ⁇ m.
  • the aspect ratio (diameter/thickness ratio) of the substrate is preferably 1-1000, in particular 3-500 and very particularly preferably 5-200.
  • the thickness of the TiO 2 layer and of the substrate, for example SiO 2 substrate, is important for the optical properties of the pigment.
  • the thickness of the layer is preferably set precisely and matched to the average thickness of the substrate platelets. Preference is given to TiO 2 layer thicknesses of 5-300 nm, preferably 10-200 nm, in particular 30-150 nm.
  • the pigments according to the invention can be prepared relatively easily by forming a high-refractive-index TiO 2 interference layer having precisely defined thickness and a smooth surface on the finely divided, platelet-shaped substrates.
  • the TiO 2 can be either in the form of rutile or in the form of anatase.
  • the TiO 2 is preferably in the rutile modification. Particular preference is given to SiO 2 platelets coated with a rutile layer.
  • the metal-oxide layer is preferably applied by wet-chemical methods, it being possible to use the wet-chemical coating methods developed for the preparation of pearlescent pigments. Methods of this type are described, for example, in DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191, DE 22 44 298, DE 23 13 331, DE 25 22 572, DE 31 37 808, DE 31 37 809, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017, and also in further patent documents and other publications known to the person skilled in the art.
  • the substrate particles are suspended in water, and one or more hydrolysable titanium salts are added at a pH which is suitable for hydrolysis, the latter being selected in such a way that the metal oxides or metal oxide hydrates are precipitated directly onto the platelets without significant secondary precipitations occurring.
  • the pH is usually kept constant by simultaneous metering-in of a base and/or acid.
  • the pigments are subsequently separated off, washed and dried at 50-150° C. and, if desired, calcined for 0.5-3 hours, where the calcination temperature can be optimised with respect to the coating present in each case.
  • the calcination temperatures are between 250 and 1000° C., preferably between 350 and 950° C.
  • the coating can furthermore also be carried out in a fluidised-bed reactor by gas-phase coating, it being possible, for example, correspondingly to use the processes proposed in EP 0 045 851 A1 and EP 0 106 235 A1 for the preparation of pearlescent pigments.
  • the pigments of the invention can also be prepared by hydrolytic decomposition of metal salts in aqueous medium or by thermal decomposition by a CVD or PVD process.
  • the hue of the pigments can be varied within very broad limits while retaining the silver effect by choosing different covering amounts or layer thicknesses resulting therefrom.
  • the fine tuning for a certain hue can be achieved beyond the pure choice of amount by approaching the desired color under visual or measurement technology control.
  • Suitable post-coatings or post-treatments are the processes described, for example, in German Patent 22 15 191, DE-A 31 51 354, DE-A 32 35 017 and DE-A 33 34 598. This post-coating further increases the chemical stability or simplifies handling of the pigment, in particular incorporation into various media.
  • functional coatings of Al 2 O 3 or ZrO 2 or mixtures or mixed phases thereof may be applied to the pigment surface furthermore, organic or combined organic/inorganic post-coatings are possible, for example with silanes, as described, for example, in EP 0090259, EP 0 634 459, WO 99/57204, WO 96/32446, WO 99/57204, U.S. Pat. No. 5,759,255, U.S. Pat. No. 5,571,851, WO 01/92425 or in J. J. Ponjeé, Philips Technical Review, Vol. 44, No. 3, 81 ff., and P. H. Harding J. C. Berg, J. Adhesion Sci. Technol. Vol.11 No. 4, pp. 471-493.
  • the silver pigments according to the invention are simple and easy to handle.
  • the pigments can be incorporated into the application system by simple stirring-in. Complex grinding and dispersal of the pigments is not necessary.
  • the silver pigments according to the invention combine high gloss with high transparency and a pure-white body color, they enable particularly effective effects to be achieved in the various application media without the absorption color being significantly affected.
  • the interference pigments can also advantageously be used in the form of a mixture with organic dyes, organic pigments or other pigments, such as, for example, transparent and opaque white, colored and black pigments, and with platelet-shaped iron oxides, organic pigments, holographic pigments, LCPs (liquid crystal polymers) and conventional transparent, colored and black Luster pigments based on metal oxide-coated mica and SiO 2 platelets, etc.
  • the interference pigments can be mixed in any ratio with commercially available pigments and fillers.
  • the pigment according to the invention can also be combined with further colorants of any type, for example organic and/or inorganic absorption pigments and dyes, multilayered interference pigments, such as, for example, Timiron®, Sicopearl® (BASF AG), ChromaFlair® (Flex Products Inc.), BiOCl pigments, pearl essence or metal pigments, for example from Eckart.
  • multilayered interference pigments such as, for example, Timiron®, Sicopearl® (BASF AG), ChromaFlair® (Flex Products Inc.), BiOCl pigments, pearl essence or metal pigments, for example from Eckart.
  • the pigments according to the invention are compatible with a multiplicity of color systems, preferably from the area of paints, coatings and printing inks.
  • a multiplicity of binders in particular water-soluble grades, as marketed, for example, by BASF, Marabu, Pröll, Sericol, Hartmann, Gebr. Schmidt, Sicpa, Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH, are suitable.
  • the printing inks may be water-based or solvent-based.
  • the pigments are furthermore also suitable for the laser marking of paper and plastics and for applications in the agricultural sector, for example for greenhouse sheeting, and, for example, for the coloring of tent awnings.
  • the silver pigment according to the invention can be used for the pigmenting of surface coatings, printing inks, plastics, agricultural sheeting, seed coatings, food colorings, button pastes, medicament coatings or cosmetic formulations, such as lipsticks, nail varnishes, compact powders, shampoos, loose powders and gels.
  • concentration of the pigment mixture in the application system to be pigmented is generally between 0.1 and 70% by weight, preferably between 0.1 and 50% by weight and in particular between 0.5 and 10% by weight, based on the total solids content of the system. It is generally dependent on the specific application.
  • Plastics comprising the silver pigment according to the invention in amounts of from 0.01 to 50% by weight, in particular from 0.1 to 7% by weight, are frequently distinguished by a particularly pronounced sparkle effect.
  • the silver pigment is also employed for three-coat systems in amounts of 0.1-10% by weight, preferably from 1 to 3% by weight.
  • the pigment according to the invention has the advantage that the target gloss is achieved by a one-coat finish (one-coat system or base coat in two-coat systems). Compared with finishes comprising a mica-based multilayered pigment instead of the silver pigment according to the invention, finishes comprising the pigment according to the invention exhibit a clearer depth effect and a more highly pronounced gloss effect.
  • the silver pigment according to the invention can also advantageously be employed in decorative and care cosmetics.
  • the use concentration extends from 0.01% by weight in shampoos to 100% by weight in the case of loose powders.
  • the concentration can be 0.01-70% by weight in the formulation.
  • the cosmetic products such as, for example, nail varnishes, lipsticks, compact powders, shampoos, loose powders and gels, are distinguished by particularly interesting gloss effects.
  • the sparkle effect in nail varnish can be significantly increased compared with conventional nail varnishes with the aid of the pigments according to the invention.
  • the pigment according to the invention can be employed in bath additives, toothpastes and for the finishing of foods, for example mass coloring and/or coatings of boiled sweets, wine gums, such as, for example, jelly babies, pralines, liquorice, confectionery, sticks of rock, fizzy drinks, sodas, etc., or as a coating, for example, in standard and coated tablets in the pharmaceuticals sector.
  • the pigment according to the invention can furthermore be mixed with commercially available fillers.
  • Fillers which may be mentioned are, for example, natural and synthetic mica, nylon powder, pure or filled melamine resins, talc, glasses, kaolin, oxides or hydroxides of aluminium, magnesium, calcium, zinc, BiOCl, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, carbon, and physical or chemical combinations of these substances.
  • the particle shape of the filler It can be, for example, platelet-shaped, spherical or needle-shaped in accordance with requirements.
  • pigments according to the invention are combined in the formulations with cosmetic raw materials and assistants of any type.
  • cosmetic raw materials and assistants include, inter alia, oils, fats, waxes, film formers, preservatives and assistants which generally determine the technical properties, such as, for example, thickeners and Theological additives, such as, for example, bentonites, hectorites, silicon dioxides, Ca silicates, gelatins, high-molecular-weight carbohydrates and/or surface-active assistants, etc.
  • the formulations comprising the pigments according to the invention can belong to the lipophilic, hydrophilic or hydrophobic type.
  • the pigments according to the invention may in each case be present in only one of the two phases or alternatively distributed over both phases.
  • the pH values of the formulations can be between 1 and 14, preferably between 2 and 11 and particularly preferably between 5 and 8.
  • concentrations of the pigments according to the invention in the formulation can be—depending on the application—between 0.001 (rinse-off products, for example shower gels) and 100% (for example gloss-effect articles for particular applications).
  • the pigments according to the invention may furthermore also be combined with cosmetic active ingredients.
  • Suitable active ingredients are, for example, insect repellents, UV A/BC protective filters (for example OMC, B3 and MBC), anti-ageing active ingredients, vitamins and derivatives thereof (for example vitamin A, C, E, etc.), self-tanning agents (for example DHA, erythrulose, inter alia), and further cosmetic active ingredients, such as, for example, bisabolol, LPO, ectoin, emblica, allantoin, bioflavonoids and derivatives thereof.
  • the use of the interference pigments according to the invention in the form of highly pigmented pastes, granules, pellets, etc. has proven particularly suitable.
  • the pigment is generally incorporated into the printing ink in amounts of 2-35% by weight, preferably 5-25% by weight and in particular 8-20% by weight.
  • Offset printing inks can comprise the pigments in amounts of up to 40% by weight or more.
  • the precursors for printing inks for example in the form of granules, as pellets, briquettes, etc., comprise up to 98% by weight of the pigment according to the invention in addition to the binder and additives.
  • Printing inks comprising the pigment according to the invention exhibit purer silver hues than with conventional effect pigments.
  • the particle thicknesses of the pigments according to the invention are relatively small and therefore effect particularly good printability.
  • interference pigments according to the invention are furthermore suitable for the preparation of flowable pigment compositions and dry preparations, in particular for printing inks, comprising one or more silver pigments according to the invention, binders and optionally one or more additives.
  • the invention thus also relates to formulations comprising the silver pigment according to the invention.
  • SiO 2 platelets 100 g of SiO 2 platelets (particle size 5-50 ⁇ m, average thickness 450 nm, standard deviation of the thickness: 5%) are suspended in 2 l of deinonized water and heated to 80° C. with vigorous stirring. A solution of 12 g of SnCl 4 ⁇ 5 H 2 O and 40 ml of hydrochloric acid (37%) in 360 ml of deinonized water is metered into this mixture at pH 1.6 at a rate of 4 ml/min. 370 ml of TiCl 4 solution (400 g of TiCl 4 /l) are subsequently metered in at a pH of 1.6 at a rate of 2 ml/min.
  • the pH is kept constant during the addition of both the SnCl 4 ⁇ 5 H 2 O solution and TiCl 4 solutions using NaOH solution (32%).
  • the pH is subsequently adjusted to 5.0 using sodium hydroxide solution (32%), and the mixture is stirred for a further 15 minutes.
  • the pigment is filtered off, washed with 20 l of deinonized water, dried at 110° C. and calcined at 850° C. for 30 minutes.
  • the product is a silver interference pigment having a slight green tint which shifts via red-violet to gold-green when viewed at an angle.
  • SiO 2 platelets 100 g of SiO 2 platelets (particle size 5-50 ⁇ m, average thickness 450 nm, standard deviation of the thickness: 5%) are suspended in 2 l of deinonized water and heated to 80° C. with vigorous stirring. A solution of 12 g of SnCl 4 ⁇ 5 H 2 O and 40 ml of hydrochloric acid (37%) in 360 ml of deinonized water is metered into this mixture at pH 1.6 at a rate of 4 ml/min. 350 ml of TiCl 4 solution (400 g of TiCl 4 /l) are subsequently metered in at a pH of 1.6 at a rate of 2 ml/min.
  • the pH is kept constant during the addition of both the SnCl 4 ⁇ 5 H 2 O solution and TiCl 4 solutions using NaOH solution (32%).
  • the pH is subsequently adjusted to 5.0 using sodium hydroxide solution (32%), and the mixture is stirred for a further 15 minutes.
  • the pigment is filtered off, washed with 20 l of deinonized water, dried at 110° C. and calcined at 850° C. for 30 minutes.
  • the product is a silver interference pigment whose color shifts via red-violet to gold-yellow when viewed at an angle.
  • SiO 2 platelets 100 g of SiO 2 platelets (particle size 5-50 ⁇ m, average thickness 450 nm, standard deviation of the thickness: 5%) are suspended in 2 l of deinonized water and heated to 80° C. with vigorous stirring. A solution of 12 g of SnCl 4 ⁇ 5 H 2 O and 40 ml of hydrochloric acid (37%) in 360 ml of deinonized water is metered into this mixture at pH 1.6 at a rate of 4 ml/min. 340 ml of TiCl 4 solution (400 g of TiCl 4 /l) are subsequently metered in at a pH of 1.6 at a rate of 2 ml/min.
  • the pH is kept constant during the addition of both the SnCl 4 ⁇ 5 H 2 O solution and TiCl 4 solutions using NaOH solution (32%).
  • the pH is subsequently adjusted to 5.0 using sodium hydroxide solution (32%), and the mixture is stirred for a further 15 minutes.
  • the pigment is filtered off, washed with 20 l of deinonized water, dried at 110° C. and calcined at 850° C. for 30 minutes.
  • the product is a silver interference pigment whose color shifts via red to gold-green when viewed at an angle.
  • phase C Melt and stir all constituents of phase C at about 75° C. until everything has melted. Initially introduce the water of phase B cold, homogenize in the Blanose using the Turrax, scatter in the Veegum, and re-homogenize. Warm to 75° C. and dissolve the other constituents therein with stirring. Stir in the constituents of phase A. Add phase C at 75° C. with stirring and homogenize for 2 minutes. Cool the mixture to 40° C. with stirring, add phase D. Cool further to room temperature with stirring and adjust to pH 6.0-6.5 (for example using citric acid solution).
  • phase A stir the pigment into the water. Slowly scatter in the Keltril T with stirring and stir until it has dissolved. Add phases B and C successively while stirring slowly until everything is homogeneously distributed. Adjust the pH to from 6.0 to 6.4.
  • Disperse the effect pigments and Ronasphere® in the water of phase A Acidify using a few drops of citric acid in order to reduce the viscosity, scatter in the Carbopol with stirring. After complete dissolution, slowly stir in the pre-dissolved phase B and adjust the pH to from 7.0 to 7.5.
  • phase A Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are pressed at from 40 to 50 bar.
  • Disperse the effect pigments and Ronasphere® in the water of phase A Acidify using a few drops of citric acid in order to reduce the viscosity, scatter in the Carbopol with stirring. After complete dissolution, slowly stir in the pre-dissolved phase B.
  • phase A Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are pressed at from 40 to 50 bar.
  • the pigment is weighed out together with the varnish base, mixed well by hand using a spatula and subsequently stirred at 1000 rpm for 10 minutes.
  • Candelilla Cera 3.50 (Candelilla Wax) Amerchol L 101 Amerchol Lanolin Alcohol, 3.00 Paraffinum Liquidum (Mineral Oil) Rohagit S Rohm GmbH Acrylates Copolymer 1.50 Beeswax white Merck KGaA/Rona ® Cera Alba (Beeswax) 1.00 Propyl 4-hydroxy- Merck KGaA/Rona ® Propylparaben 0.10 benzoate Oxynex ® K liquid Merck KGaA/Rona ® PEG-8, Tocopherol, 0.05 Ascorbyl Palmitate, Ascorbic Acid, Citric Acid Phase C Fragrance Tendresse # Haarmann & Perfume 0.10 75418C Reimer GmbH Preparation: Warm all constituents (apart from the Foral 85-E) of phase B to 80° C. and slowly add the Foral 85-E with stirring. Add phase A and phase C to the molten phase B. Pour the homogeneous melt into the mould

Abstract

The present invention relates to silver pigments based on transparent, low-refractive-index, platelet-shaped substrates which have a high-refractive-index coating consisting of TiO2 having a layer thickness of 5-300 nm and optionally an outer protective layer, and to the use thereof in paints, coatings, printing inks, security printing inks, plastics, button pastes, ceramic materials, glasses, for seed coloring, as dopants in the laser marking of plastics and papers, as additives for coloring in the foods and pharmaceuticals sectors, and in cosmetic formulations and for the preparation of pigment compositions and dry preparations.

Description

The present invention relates to silver interference pigments based on platelet-shaped, transparent, low-refractive-index substrates and to the use thereof in paints, coatings, printing inks, plastics, as dopants for the laser marking of plastics and papers, as additives in the foods and pharmaceuticals sectors and in cosmetic formulations.
Luster or effect pigments are employed in many areas of industry, in particular in the area of automotive finishes, decorative coatings, plastics, paints, printing inks and in cosmetic formulations.
Owing to their color play, Luster pigments, which exhibit an angle-dependent color change between a plurality of interference colors, are of particular interest for automotive finishes and in forgery-proof documents of value.
Mineral-based pearlescent pigments are of particular importance. Pearlescent pigments are prepared by coating an inorganic, platelet-shaped support with a high-refractive-index, usually oxidic layer. The color of these pigments is caused by wavelength-selective partial reflection and interference of the reflected or transmitted light at the medium/oxide or oxide/substrate interfaces.
The interference color of these pigments is determined by the thickness of the oxide layer. The hue of a silver pigment is generated by a (in the optical sense) single high-refractive-index layer whose optical thickness causes a reflection maximum (1st order) in the visible wavelength range at about 500 nm. This wavelength is perceived by the human eye as the color green. However, the intensity curve of this maximum on its wavelength axis is so broad that so much light is reflected throughout the region of visible light that the human eye perceives a very bright, but colorless impression.
According to the known rules—in particular from the coating of optical components—of the optics of thin layers, the intensity of the reflected light in an arrangement of a plurality of layers with alternating high and low refractive indexes increases greatly compared with a single layer. Thus, the application of a TiO2—SiO2—TiO2 layer system to mica particles increases the intensity of the reflected light by about 60% compared with a TiO2 single-layer system. Accordingly, the profile of the light reflected by interference is significantly more pronounced, so that an intense and bright reflection color must be expected for a multilayered system of this type. Pigments of this type are described in DE 196 18 569 A1.
The prior art discloses silver pigments based on mica platelets which have a very broad scattering of the layer thickness and therefore have a neutral behavior with respect to the interference color. Pearlescent pigments that have a single high-refractive-index coating of mica therefore represent single-layer optical systems, i.e. the interference color is determined exclusively by the layer thickness of the high-refractive-index metal-oxide layer. The coloristic design latitude of a mica/metal oxide silver pigment is therefore very restricted.
In addition, mica particles, owing to their layer structure, have irregularities on the surface which cause scattering and thus reduce the transparency and coloristic quality of the product. Furthermore, mica exhibits a more or less highly pronounced grey-brown body color. This property reduces the transparency further and influences the absorption color of the application media in an undesired manner.
Furthermore, multilayered pigments which cause a silver color impression, as described, for example, in EP 1213330 A1, are known. In the case of these pigments, an intense color can be suppressed by the SiO2 layer of the TiO2—SiO2—TiO2 layer sequence having been applied very thinly (about 50 nm). These pigments, like the single-layered mica-based silver pigments, offer only a very small latitude in the design of the coloristic properties and have the above-mentioned disadvantages of mica as substrate.
The object of the present invention is therefore to provide a silver-colored interference pigment which is distinguished, in particular, by high transparency, a pure-white body color and coloristic design possibilities which go beyond an exclusively silver effect.
Surprisingly, it has now been found that a specific transparent, low-refractive-index platelet, such as, for example, an SiO2 platelet, coated with a thin TiO2 layer causes a silver color impression. This is achieved through the coating of the platelet with a TiO2 layer whose thickness is “matched” precisely to the thickness of the platelet.
The interference color of a thin layer is determined by its thickness. In a lamellar thin layer system like coated thin platelets the color is a result of the reflection of the whole stack of layers as one reflection system.
On substrates with somewhat different mean thickness similar color effects can be achieved by “matching” of the thickness of the titanium dioxide coating. This is done by color measurements during the coating process and interruption of the coating process when the desired color on the respective substrate is obtained.
To maintain the described silver color effect on substrates with different mean thickness it is necessary to choose an individual coating thickness for every particular substrate thickness. This is also done by the above described matching of coating thickness.
Compared with single-coated mica-based silver pigments and the interference pigments from EP 1213330 A1, the pigments according to the invention exhibit the following properties:
    • excellent transparency in the application medium
    • pure-white body color
    • very bright silver interference color.
In addition to these properties, the pigments according to the invention are distinguished over the known interference pigments by the following features:
    • strong sparkle effect
    • adjustable hue
    • angle-dependence of the hue
The said hue can be varied over a broad range by adjusting (i.e., “matching”) the TiO2 layer thickness and through the choice of transparent platelets, such as, for example, SiO2 platelets, of various thickness without losing the impression of an interference pigment. Such matching as described above, is conventional.
The invention therefore relates to silver interference pigments based on platelet-shaped, transparent, low-refractive-index substrates which have a high-refractive-index coating consisting of TiO2 having a layer thickness of 5-300 nm and optionally an outer protective layer.
The invention furthermore relates to the use of the silver pigments according to the invention in paints, coatings, printing inks, plastics, button pastes, ceramic materials, glasses, for seed coating, as dopants in the laser marking of plastics and papers, as additives for coloring in the foods and pharmaceuticals sectors and in particular in cosmetic formulations. The pigments according to the invention are furthermore also suitable for the preparation of pigment compositions and for the preparation of dry preparations, such as, for example, granules, chips, pellets, briquettes, etc. The dry preparations are particularly suitable for printing inks and for cosmetic formulations.
Suitable substrates are all low refractive index inorganic and organic transparent materials which can be produced in the form of finely divided platelets having a narrow thickness distribution. Suitable organic substrates are, inter alia, polymers, such as, for example, polyesters (for example PET), polycarbonates, polyimides and polymethacrylates.
Suitable base substrates for the interference pigments according to the invention are substrates having a refractive index of <1.9, for example platelet-shaped SiO2 platelets, as described, for example, in WO 93/08237. Furthermore, besides the said SiO2 platelets, any platelet-shaped, transparent substrate known to the person skilled in the art, such as, for example, Al2O3 platelets, glass platelets and platelet-shaped plastic particles, is suitable. Very particularly preferred substrates are SiO2 platelets. The particular properties, such as the tuneable hue and in particular the angle dependence thereof, are particularly supported by a defined average density with a narrow thickness distribution.
Particular preference is given to the production of interference pigments based on substrates of SiO2, Al2O3, all single crystals with a flaky appearance and glass platelets, all coated with a thin titanium dioxide layer.
The standard deviation of the thickness of the substrate platelets is therefore ≦20%, more preferably ≦10% and particularly preferably ≦5%, based on the average layer thickness thereof.
“Low” refractive index is understood in the art to refer to materials with refractive index ≦1.9, while “high” refractive index refers to >1.9.
The size of the base substrate is not crucial per se and can be matched to the particular application. In general, the platelet-shaped transparent substrates have an average thickness of between 0.02 and 10 μm, preferably between 0.03 and 5 μm, in particular between 0.05 and 3 μm. The size in the two other dimensions is usually between 1 and 450 μm, preferably between 2 and 200 μm and in particular between 5 and 100 μm.
The aspect ratio (diameter/thickness ratio) of the substrate is preferably 1-1000, in particular 3-500 and very particularly preferably 5-200.
The thickness of the TiO2 layer and of the substrate, for example SiO2 substrate, is important for the optical properties of the pigment. The thickness of the layer is preferably set precisely and matched to the average thickness of the substrate platelets. Preference is given to TiO2 layer thicknesses of 5-300 nm, preferably 10-200 nm, in particular 30-150 nm.
The pigments according to the invention can be prepared relatively easily by forming a high-refractive-index TiO2 interference layer having precisely defined thickness and a smooth surface on the finely divided, platelet-shaped substrates. The TiO2 can be either in the form of rutile or in the form of anatase. The TiO2 is preferably in the rutile modification. Particular preference is given to SiO2 platelets coated with a rutile layer.
The metal-oxide layer is preferably applied by wet-chemical methods, it being possible to use the wet-chemical coating methods developed for the preparation of pearlescent pigments. Methods of this type are described, for example, in DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191, DE 22 44 298, DE 23 13 331, DE 25 22 572, DE 31 37 808, DE 31 37 809, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017, and also in further patent documents and other publications known to the person skilled in the art.
In the case of wet coating, the substrate particles are suspended in water, and one or more hydrolysable titanium salts are added at a pH which is suitable for hydrolysis, the latter being selected in such a way that the metal oxides or metal oxide hydrates are precipitated directly onto the platelets without significant secondary precipitations occurring. The pH is usually kept constant by simultaneous metering-in of a base and/or acid. The pigments are subsequently separated off, washed and dried at 50-150° C. and, if desired, calcined for 0.5-3 hours, where the calcination temperature can be optimised with respect to the coating present in each case. In general, the calcination temperatures are between 250 and 1000° C., preferably between 350 and 950° C.
The coating can furthermore also be carried out in a fluidised-bed reactor by gas-phase coating, it being possible, for example, correspondingly to use the processes proposed in EP 0 045 851 A1 and EP 0 106 235 A1 for the preparation of pearlescent pigments. Thus, the pigments of the invention can also be prepared by hydrolytic decomposition of metal salts in aqueous medium or by thermal decomposition by a CVD or PVD process.
The hue of the pigments can be varied within very broad limits while retaining the silver effect by choosing different covering amounts or layer thicknesses resulting therefrom. The fine tuning for a certain hue can be achieved beyond the pure choice of amount by approaching the desired color under visual or measurement technology control.
In order to increase the light, water and weather stability, it is frequently advisable, depending on the area of application, to subject the finished pigment to post-coating or post-treatment. Suitable post-coatings or post-treatments are the processes described, for example, in German Patent 22 15 191, DE-A 31 51 354, DE-A 32 35 017 and DE-A 33 34 598. This post-coating further increases the chemical stability or simplifies handling of the pigment, in particular incorporation into various media. In order to improve the wettability, dispersibility and/or compatibility with the application media, functional coatings of Al2O3 or ZrO2 or mixtures or mixed phases thereof may be applied to the pigment surface furthermore, organic or combined organic/inorganic post-coatings are possible, for example with silanes, as described, for example, in EP 0090259, EP 0 634 459, WO 99/57204, WO 96/32446, WO 99/57204, U.S. Pat. No. 5,759,255, U.S. Pat. No. 5,571,851, WO 01/92425 or in J. J. Ponjeé, Philips Technical Review, Vol. 44, No. 3, 81 ff., and P. H. Harding J. C. Berg, J. Adhesion Sci. Technol. Vol.11 No. 4, pp. 471-493.
The silver pigments according to the invention are simple and easy to handle. The pigments can be incorporated into the application system by simple stirring-in. Complex grinding and dispersal of the pigments is not necessary.
Since the silver pigments according to the invention combine high gloss with high transparency and a pure-white body color, they enable particularly effective effects to be achieved in the various application media without the absorption color being significantly affected.
It goes without saying that, for the various applications, the interference pigments can also advantageously be used in the form of a mixture with organic dyes, organic pigments or other pigments, such as, for example, transparent and opaque white, colored and black pigments, and with platelet-shaped iron oxides, organic pigments, holographic pigments, LCPs (liquid crystal polymers) and conventional transparent, colored and black Luster pigments based on metal oxide-coated mica and SiO2 platelets, etc. The interference pigments can be mixed in any ratio with commercially available pigments and fillers.
In the various applications, the pigment according to the invention can also be combined with further colorants of any type, for example organic and/or inorganic absorption pigments and dyes, multilayered interference pigments, such as, for example, Timiron®, Sicopearl® (BASF AG), ChromaFlair® (Flex Products Inc.), BiOCl pigments, pearl essence or metal pigments, for example from Eckart. There are no limits to the mixing ratios and concentration.
The pigments according to the invention are compatible with a multiplicity of color systems, preferably from the area of paints, coatings and printing inks. For the production of printing inks for, for example, gravure printing, flexographic printing, offset printing or offset overprinting, a multiplicity of binders, in particular water-soluble grades, as marketed, for example, by BASF, Marabu, Pröll, Sericol, Hartmann, Gebr. Schmidt, Sicpa, Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH, are suitable. The printing inks may be water-based or solvent-based. The pigments are furthermore also suitable for the laser marking of paper and plastics and for applications in the agricultural sector, for example for greenhouse sheeting, and, for example, for the coloring of tent awnings.
The silver pigment according to the invention can be used for the pigmenting of surface coatings, printing inks, plastics, agricultural sheeting, seed coatings, food colorings, button pastes, medicament coatings or cosmetic formulations, such as lipsticks, nail varnishes, compact powders, shampoos, loose powders and gels. The concentration of the pigment mixture in the application system to be pigmented is generally between 0.1 and 70% by weight, preferably between 0.1 and 50% by weight and in particular between 0.5 and 10% by weight, based on the total solids content of the system. It is generally dependent on the specific application.
Plastics comprising the silver pigment according to the invention in amounts of from 0.01 to 50% by weight, in particular from 0.1 to 7% by weight, are frequently distinguished by a particularly pronounced sparkle effect.
In the surface coatings sector, in particular in automotive paints, the silver pigment is also employed for three-coat systems in amounts of 0.1-10% by weight, preferably from 1 to 3% by weight.
In surface coatings, the pigment according to the invention has the advantage that the target gloss is achieved by a one-coat finish (one-coat system or base coat in two-coat systems). Compared with finishes comprising a mica-based multilayered pigment instead of the silver pigment according to the invention, finishes comprising the pigment according to the invention exhibit a clearer depth effect and a more highly pronounced gloss effect.
The silver pigment according to the invention can also advantageously be employed in decorative and care cosmetics. The use concentration extends from 0.01% by weight in shampoos to 100% by weight in the case of loose powders. In the case of a mixture of the silver pigments with spherical fillers, for example SiO2, the concentration can be 0.01-70% by weight in the formulation. The cosmetic products, such as, for example, nail varnishes, lipsticks, compact powders, shampoos, loose powders and gels, are distinguished by particularly interesting gloss effects. The sparkle effect in nail varnish can be significantly increased compared with conventional nail varnishes with the aid of the pigments according to the invention. Furthermore, the pigment according to the invention can be employed in bath additives, toothpastes and for the finishing of foods, for example mass coloring and/or coatings of boiled sweets, wine gums, such as, for example, jelly babies, pralines, liquorice, confectionery, sticks of rock, fizzy drinks, sodas, etc., or as a coating, for example, in standard and coated tablets in the pharmaceuticals sector.
The pigment according to the invention can furthermore be mixed with commercially available fillers. Fillers which may be mentioned are, for example, natural and synthetic mica, nylon powder, pure or filled melamine resins, talc, glasses, kaolin, oxides or hydroxides of aluminium, magnesium, calcium, zinc, BiOCl, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, carbon, and physical or chemical combinations of these substances. There are no restrictions regarding the particle shape of the filler. It can be, for example, platelet-shaped, spherical or needle-shaped in accordance with requirements.
It is of course also possible for the pigments according to the invention to be combined in the formulations with cosmetic raw materials and assistants of any type. These include, inter alia, oils, fats, waxes, film formers, preservatives and assistants which generally determine the technical properties, such as, for example, thickeners and Theological additives, such as, for example, bentonites, hectorites, silicon dioxides, Ca silicates, gelatins, high-molecular-weight carbohydrates and/or surface-active assistants, etc.
The formulations comprising the pigments according to the invention can belong to the lipophilic, hydrophilic or hydrophobic type. In the case of heterogeneous formulations having discrete aqueous and non-aqueous phases, the pigments according to the invention may in each case be present in only one of the two phases or alternatively distributed over both phases.
The pH values of the formulations can be between 1 and 14, preferably between 2 and 11 and particularly preferably between 5 and 8.
No limits are set for the concentrations of the pigments according to the invention in the formulation. They can be—depending on the application—between 0.001 (rinse-off products, for example shower gels) and 100% (for example gloss-effect articles for particular applications).
The pigments according to the invention may furthermore also be combined with cosmetic active ingredients. Suitable active ingredients are, for example, insect repellents, UV A/BC protective filters (for example OMC, B3 and MBC), anti-ageing active ingredients, vitamins and derivatives thereof (for example vitamin A, C, E, etc.), self-tanning agents (for example DHA, erythrulose, inter alia), and further cosmetic active ingredients, such as, for example, bisabolol, LPO, ectoin, emblica, allantoin, bioflavonoids and derivatives thereof.
In the pigmenting of binder systems, for example for surface coatings and printing inks for gravure printing, offset printing or screen printing, or as precursors for printing inks, the use of the interference pigments according to the invention in the form of highly pigmented pastes, granules, pellets, etc., has proven particularly suitable. The pigment is generally incorporated into the printing ink in amounts of 2-35% by weight, preferably 5-25% by weight and in particular 8-20% by weight. Offset printing inks can comprise the pigments in amounts of up to 40% by weight or more. The precursors for printing inks, for example in the form of granules, as pellets, briquettes, etc., comprise up to 98% by weight of the pigment according to the invention in addition to the binder and additives. Printing inks comprising the pigment according to the invention exhibit purer silver hues than with conventional effect pigments. The particle thicknesses of the pigments according to the invention are relatively small and therefore effect particularly good printability.
The interference pigments according to the invention are furthermore suitable for the preparation of flowable pigment compositions and dry preparations, in particular for printing inks, comprising one or more silver pigments according to the invention, binders and optionally one or more additives.
The invention thus also relates to formulations comprising the silver pigment according to the invention.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
In the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
EXAMPLES Example 1 Silver Pigment with Color Travel from Green Via Red-Violet to Gold-Green
100 g of SiO2 platelets (particle size 5-50 μm, average thickness 450 nm, standard deviation of the thickness: 5%) are suspended in 2 l of deinonized water and heated to 80° C. with vigorous stirring. A solution of 12 g of SnCl4×5 H2O and 40 ml of hydrochloric acid (37%) in 360 ml of deinonized water is metered into this mixture at pH 1.6 at a rate of 4 ml/min. 370 ml of TiCl4 solution (400 g of TiCl4/l) are subsequently metered in at a pH of 1.6 at a rate of 2 ml/min. The pH is kept constant during the addition of both the SnCl4×5 H2O solution and TiCl4 solutions using NaOH solution (32%). The pH is subsequently adjusted to 5.0 using sodium hydroxide solution (32%), and the mixture is stirred for a further 15 minutes.
For work-up, the pigment is filtered off, washed with 20 l of deinonized water, dried at 110° C. and calcined at 850° C. for 30 minutes. The product is a silver interference pigment having a slight green tint which shifts via red-violet to gold-green when viewed at an angle.
Example 2 Silver Pigment with Color Travel from Neutral Silver Via Red-Violet to Gold-Yellow
100 g of SiO2 platelets (particle size 5-50 μm, average thickness 450 nm, standard deviation of the thickness: 5%) are suspended in 2 l of deinonized water and heated to 80° C. with vigorous stirring. A solution of 12 g of SnCl4×5 H2O and 40 ml of hydrochloric acid (37%) in 360 ml of deinonized water is metered into this mixture at pH 1.6 at a rate of 4 ml/min. 350 ml of TiCl4 solution (400 g of TiCl4/l) are subsequently metered in at a pH of 1.6 at a rate of 2 ml/min. The pH is kept constant during the addition of both the SnCl4×5 H2O solution and TiCl4 solutions using NaOH solution (32%). The pH is subsequently adjusted to 5.0 using sodium hydroxide solution (32%), and the mixture is stirred for a further 15 minutes. For work-up, the pigment is filtered off, washed with 20 l of deinonized water, dried at 110° C. and calcined at 850° C. for 30 minutes. The product is a silver interference pigment whose color shifts via red-violet to gold-yellow when viewed at an angle.
Example 3 Silver Pigment with Color Travel from Slightly Bluish Silver Via Red to Gold-Green
100 g of SiO2 platelets (particle size 5-50 μm, average thickness 450 nm, standard deviation of the thickness: 5%) are suspended in 2 l of deinonized water and heated to 80° C. with vigorous stirring. A solution of 12 g of SnCl4×5 H2O and 40 ml of hydrochloric acid (37%) in 360 ml of deinonized water is metered into this mixture at pH 1.6 at a rate of 4 ml/min. 340 ml of TiCl4 solution (400 g of TiCl4/l) are subsequently metered in at a pH of 1.6 at a rate of 2 ml/min. The pH is kept constant during the addition of both the SnCl4×5 H2O solution and TiCl4 solutions using NaOH solution (32%). The pH is subsequently adjusted to 5.0 using sodium hydroxide solution (32%), and the mixture is stirred for a further 15 minutes.
For work-up, the pigment is filtered off, washed with 20 l of deinonized water, dried at 110° C. and calcined at 850° C. for 30 minutes. The product is a silver interference pigment whose color shifts via red to gold-green when viewed at an angle.
Use Example Example A Shimmering Foundation
Raw material Source of supply INCI [%]
Phase A
Extender W Merck KGaA/Rona ® MICA, CI 77891 9.00
(Titanium Dioxide)
MICRONA ® Matte Yellow Merck KGaA/Rona ® MICA, CI 77492 (Iron 4.00
Oxides)
MICRONA ® Matte Red Merck KGaA/Rona ® MICA, CI 77491 (Iron 0.40
Oxides)
MICRONA ® Matte Black Merck KGaA/Rona ® MICA, CI 77499 (Iron 0.30
Oxides)
Pigment from Example 1 Merck KGaA 4.50
RONASPHERE ® Merck KGaA/Rona ® SILICA 5.00
Phase B
Blanose 7 HF Aqualon GmbH Cellulose Gum 0.20
Veegum Vanderbilt Magnesium Aluminium 1.00
Silicate
Texapon K 1296 Cognis GmbH Sodium Lauryl Sulfate 0.60
Triethanolamine extra Merck KGaA/Rona ® Triethanolamine 0.50
pure
Titriplex III Merck KGaA/Rona ® Disodium EDTA 0.25
Methyl 4-hydroxy- Merck KGaA/Rona ® Methylparaben 0.15
benzoate
1,2-Propanediol Merck KGaA/Rona ® Propylene Glycol 10.90
Water, demineralised Aqua (Water) 42.95
Phase C
Isopropyl myristate Cognis GmbH Isopropyl Myristate 8.00
Liquid paraffin Merck KGaA/Rona ® Paraffinum Liquidum 3.60
(Mineral Oil)
Crodamol SS Croda GmbH Cetyl Esters 2.60
Monomuls 60-35 C Cognis GmbH Hydrogenated Palm 1.70
Glycerides
Stearic acid Merck KGaA/Rona ® Stearic Acid 1.50
EUSOLEX ® 6300 Merck KGaA/Rona ® 4-Methylbenzylidene 1.30
Camphor
EUSOLEX ® 4360 Merck KGaA/Rona ® Benzophenone-3 0.50
Rona Care ™ Merck KGaA/Rona ® Tocopheryl Acetate 0.50
Tocopherol acetate
Magnesium stearate Merck KGaA/Rona ® Magnesium Stearate 0.10
Propyl 4-hydroxy- Merck KGaA/Rona ® Propylparaben 0.05
benzoate
Phase D
Perfume oil 200 529 Fragrance Perfume 0.20
Resources
Euxyl K 400 Schülke & Mayr Phenoxyethanol, 0.20
GmbH Methyldibromo,
Glutaronitrile

Preparation:
Melt and stir all constituents of phase C at about 75° C. until everything has melted. Initially introduce the water of phase B cold, homogenize in the Blanose using the Turrax, scatter in the Veegum, and re-homogenize. Warm to 75° C. and dissolve the other constituents therein with stirring. Stir in the constituents of phase A. Add phase C at 75° C. with stirring and homogenize for 2 minutes. Cool the mixture to 40° C. with stirring, add phase D. Cool further to room temperature with stirring and adjust to pH 6.0-6.5 (for example using citric acid solution).
Example B Shower Gel
Raw material Source of supply INCI [%]
Phase A
Pigment from Example 2 Merck KGaA 0.10
Keltrol T Kelco Xanthan Gum 0.75
Water, demineralised Aqua (Water) 64.95
Phase B
Plantacare 2000 UP Cognis GmbH Decyl Glucoside 20.00
Texapon ASV 50 Cognis GmbH Sodium Laureth Sulfate, 3.60
Sodium Laureth-8
Sulfate, Magnesium
Laureth Sulfate,
Magnesium Laureth-8 Sulfate,
Sodium Oleth Sulfate,
Magnesium Oleth Sulfate
Bronidox L Cognis GmbH Propylene Glycol, 0.20
5-Bromo-5-Nitro-1,3-
Dioxane
Perfume oil Everest Haarmann & Perfume 0.05
79658 SB (deleted) Reimer GmbH
1% FD&C lue No. 1 in BASF AG Aqua (Water), CI 42090 0.20
water (FD&C Blue No. 1)
Phase C
Citric acid monohydrate Merck KGaA/Rona ® Citric Acid 0.15
Water, demineralised Aqua Water 10.00

Preparation:
For phase A, stir the pigment into the water. Slowly scatter in the Keltril T with stirring and stir until it has dissolved. Add phases B and C successively while stirring slowly until everything is homogeneously distributed. Adjust the pH to from 6.0 to 6.4.
Example C Eyeliner Gel
Raw material Source of supply INCI [%]
Phase A
Pigment from Example 3 Merck KGaA 5.00
Xirona ® Magic Mauve Merck KGaA/Rona ® Silica, CI 77891 10.00
(Titanium Dioxide), Tin
oxide
Mica Black Merck KGaA/Rona ® CI 77499 (Iron Oxides), 5.00
MICA, CI 77891
(Titanium Dioxide)
RONASPHERE ® Merck KGaA/Rona ® Silica 2.00
Carbopol ETD 2001 BF Goodrich Carbomer 0.40
Citric acid monohydrate Merck KGaA/Rona ® Citric Acid 0.00
Water, demineralised Aqua (Water) 60.00
Phase B
Glycerol, anhydrous Merck KGaA/Rona ® Glycerin 4.00
Triethanolamine extra Merck KGaA/Rona ® Triethanolamine 0.90
pure
Luviskol VA 64 Powder BASF AG PVP/VA Copolymer 2.00
Germaben II ISP Global Propylene Glycol, 1.00
Technologies Diazolidinyl Urea,
Methylparaben, Propylparaben
Water, demineralised Aqua (Water) 9.70

Preparation:
Disperse the effect pigments and Ronasphere® in the water of phase A. Acidify using a few drops of citric acid in order to reduce the viscosity, scatter in the Carbopol with stirring. After complete dissolution, slowly stir in the pre-dissolved phase B and adjust the pH to from 7.0 to 7.5.
Example D Eye Shadow
Raw material Source of supply INCI [%]
Phase A
Xirona ® Caribbean Blue Merck KGaA/Rona ® Silica, CI 77891 45.00
(Titanium Dioxide),
Mica, Tin Oxide
Mica Black Merck KGaA/Rona ® CI 77499 (Iron Oxides), 5.00
MICA, CI 77891
(Titanium Dioxide)
Pigment from Example 1 Merck KGaA 5.00
BIRON ® B 50 Merck KGaA/Rona ® CI 77163 (Bismuth Oxy-chloride) 3.00
Colorona ® Dark Blue Merck KGaA/Rona ® MICA, CI 77891 10.00
(Titanium Dioxide), CI
77510 (Ferric Ferro-cyanide)
Magnesium stearate Merck KGaA/Rona ® Magnesium Stearate 2.50
White clay (deleted) Merck KGaA/Rona ® Kaolin 5.00
Hubersorb 600 J.M. Huber Corp. Calcium Stearate 0.50
Talc Merck KGaA/Rona ® Talc 11.00
Phase B
Amerchol L 101 Amerchol Lanolin Alcohol, 10.70
Paraffinum Liquidum
(Mineral Oil)
Super Hartolan Croda GmbH Lanolin Alcohol 1.00
Ewalin 1751 H. Erhard Wagner Petrolatum 1.00
GmbH
Propyl 4-hydroxy- Merck KGaA/Rona ® Propylparaben 0.10
benzoate
Perfume oil Elegance # Haarmann & Perfume 0.20
79228 D MF Reimer GmbH

Preparation:
Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are pressed at from 40 to 50 bar.
Example E Eye Shadow Gel
Raw material Source of supply INCI [%]
Phase A
Xirona ® Indian Merck KGaA/Rona ® Silica, Cl 77491 (Iron 15.00
Summer Oxides)
Pigment from Example 3 Merck KGaA 5.00
RONASPHERE ® Merck KGaN/Rona ® SILICA 3.00
Carbopol ETD 2001 BF Goodrich GmbH CARBOMER 0.30
Citric acid monohydrate Merck KGaA/Rona ® Citric Acid 0.00
Water, demineralized Aqua (Water) 60.00
Phase B
Glycerol, anhydrous Merck KGaA/Rona ® Glycerin 2.00
Germaben II ISP Global Propylene Glycol, 0.20
Technologies Diazolidinyl Urea,
Methylparaben, Propylparaben
Triethanolamine extra Merck KGaA/Rona ® Triethanolamine 0.70
pure
Water, demineralized Aqua (Water) 13.80

Preparation:
Disperse the effect pigments and Ronasphere® in the water of phase A. Acidify using a few drops of citric acid in order to reduce the viscosity, scatter in the Carbopol with stirring. After complete dissolution, slowly stir in the pre-dissolved phase B.
Example F Eye Shadow
Raw material Source of supply INCI [%]
Phase A
Xirona ® Caribbean Blue Merck KGaA/Rona ® Silica, Cl 77891 20.00
(Titanium Dioxide),
MICA, TIN Oxide
Colorona ® Dark Blue Merck KGaA/Rona ® MICA, Cl 77891 5.00
(Titanium Dioxide), Cl
77510 (Ferric Ferro-cyanide)
Pigment from Example 2 Merck KGaA 5.00
Talc Merck KGaA/Rona ® Talc 49.50
Potato starch Sudstarke GmbH Solanum Tuberosum 7.50
(Potato Starch)
Magnesium stearate Merck KGaA/Rona ® Magnesium Stearate 2.50
Phase B
Isopropyl stearate Cognis GmbH Isopropyl Stearate 9.14
Cetyl palmitate Merck KGaA/Rona ® Cetyl Palmitate 0.53
Ewalin 1751 H. Erhard Wagner Petrolatum 0.53
GmbH
Perfume oil Elegance # Haarmann & Perfume 0.20
79228 D MF Reimer GmbH
Propyl 4-hydroxy- Merck KGaA/Rona ® Propylparaben 0.10
benzoate

Preparation:
Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are pressed at from 40 to 50 bar.
Example G Nail Varnish
Raw material Source of supply INCI [%]
Pigment from Merck KGaA 2.00
Example 1
Thixotropic International Toluene, Ethyl Acetate, 98.00
nail varnish Lacquers S.A. Butyl Acetate, Nitro-
base 1348 cellulose, Tosyl-
amide/Formaldehyde
Resin, Dibutyl
Phthalate, Isopropyl
Alcohol, Stearalkonium
Hectorite, Camphor,
Acrylates Copolymer,
Benzophenone-1

Preparation:
The pigment is weighed out together with the varnish base, mixed well by hand using a spatula and subsequently stirred at 1000 rpm for 10 minutes.
Example H Lip Lacquer
Raw material Source of supply INCI [%]
Phase A
Pigment from Example 1 Merck KGaA 2.50
Timiron ® Splendid Violet Merck KGaA/Rona ® MICA, Silica, Cl 77891 5.00
(Titanium Dioxide)
Xirona ® Indian Summer Merck KGaA/Rona ® Silica, Cl 77491 (Iron 2.50
Oxides)
Rubis Covapate W 4765 Les Colorants Ricinus Communis 5.00
Wackherr (Castor Oil), Cl 15850
(D&C Red No. 7
Calcium Lake)
Phase B
Foralyn 5020-F Hercules BV Methyl Hydrogenated 20.00
Rosinate
Adeps Lanae Henry Lamotte Lanolin 18.00
GmbH
Castor oil Henry Lamotte Ricinus Communis 13.75
GmbH (Castor Oil)
Foral 85-E Hercules BV Glyceryl Hydrogenated Rosinate 12.00
Jojoba oil Gustav Heess Buxus Chinensis 5.00
GmbH (Jojoba oil)
Eusolex ® 2292 Merck KGaA/Rona ® Ethylhexyl Methoxy- 3.00
cinnamate, BHT
Antaron V-216 ISP Global PVP/Hexadecene 4.00
Technologies Copolymer
Candelilla Wax 2039 L Kahl & Co. Candelilla Cera 3.50
(Candelilla Wax)
Amerchol L 101 Amerchol Lanolin Alcohol, 3.00
Paraffinum Liquidum
(Mineral Oil)
Rohagit S Rohm GmbH Acrylates Copolymer 1.50
Beeswax white Merck KGaA/Rona ® Cera Alba (Beeswax) 1.00
Propyl 4-hydroxy- Merck KGaA/Rona ® Propylparaben 0.10
benzoate
Oxynex ® K liquid Merck KGaA/Rona ® PEG-8, Tocopherol, 0.05
Ascorbyl Palmitate,
Ascorbic Acid, Citric
Acid
Phase C
Fragrance Tendresse # Haarmann & Perfume 0.10
75418C Reimer GmbH

Preparation:
Warm all constituents (apart from the Foral 85-E) of phase B to 80° C. and slowly add the Foral 85-E with stirring. Add phase A and phase C to the molten phase B. Pour the homogeneous melt into the mould at 50° C.
The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding German application No. 103 13 978.8, filed Mar. 27, 2003 and is incorporated by reference herein.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.

Claims (10)

1. A silver pigment, consisting of a transparent, platelet-shaped substrate, which is an SiO2 platelet, Al2O3 platelet, a polymer platelet, a single crystal or a glass platelet, having a refractive index ≦1.9, and an average thickness of individual platelets within a standard deviation of ≦20%, and on said substrate a coating of TiO2 and optionally an outer protective layer, said pigment having a silver interference color, whereby said pigment exhibits color travel.
2. A silver pigment according to claim 1, wherein the TiO2 coating has a layer thickness of 5-300 nm.
3. A silver pigment according to claim 2, wherein the transparent platelet is an SiO2 platelet.
4. A silver pigment according to claim 1, wherein the average thickness of individual platelets is within a standard deviation of ≦10%.
5. A silver pigment according to claim 1, wherein the TiO2 is in the rutile modification.
6. A process for the preparation of a silver pigment according to claim 1, comprising a coating of the substrate by wet-chemical methods, by hydrolytic decomposition of metal salts in aqueous medium or by thermal decomposition by a CVD or PVD process.
7. A process according to claim 6, wherein the TiO2 coating is matched to the substrate as to produce a silver interference color.
8. In a paint, coating, printing ink, security printing ink, plastic, button paste, ceramic material, glass, seed coating, dopant for laser marking of plastics or papers, an additive for coloring of foods or pharmaceuticals or, cosmetic formulation comprising a pigment the improvement wherein the pigment is one according to claim 1.
9. A pigment composition comprising at least one binder, at least one silver pigment according to claim 1, and optionally conventional additives.
10. A dry preparation comprising pellets, granules, chips or briquettes of a silver pigment according to claim 1.
US10/811,143 2003-03-27 2004-03-29 Silver pigments Expired - Lifetime US7344590B2 (en)

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DE10313978A DE10313978A1 (en) 2003-03-27 2003-03-27 Silver pigments based on a transparent lamellar substrate of low refractive index comprise a highly refractive titanium dioxide coating
DE10313978.8 2003-03-27

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US20070207927A1 (en) * 2006-03-01 2007-09-06 Rosa Fred C Polymer based seed coating
US20110189605A1 (en) * 2008-09-05 2011-08-04 Sukgyung AT Co., Ltd. Making Method for Titania Nanoparticle
US20110226161A1 (en) * 2009-08-19 2011-09-22 Dirk Schumacher High-gloss multilayer effect pigments having a silver interference color and a narrow size distribution, and method for the production thereof
US9168394B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
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US20060228553A1 (en) * 2002-09-13 2006-10-12 Jds Uniphase Corporation High chroma optically variable color-shifting glitter
US10822497B2 (en) 2004-02-09 2020-11-03 Merck Patent Gmbh Interference pigments
US20060272534A1 (en) * 2005-06-03 2006-12-07 Daniel Lieberman Systems and methods for printing surface relief structures
US20070207927A1 (en) * 2006-03-01 2007-09-06 Rosa Fred C Polymer based seed coating
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US20110189605A1 (en) * 2008-09-05 2011-08-04 Sukgyung AT Co., Ltd. Making Method for Titania Nanoparticle
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US9168394B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9168393B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9168209B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9320687B2 (en) 2013-03-13 2016-04-26 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US11274211B2 (en) * 2017-04-27 2022-03-15 Nippon Sheet Glass Company, Limited Glitter pigment having electromagnetic wave transmission properties, composition including the pigment, and painted product including the pigment

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US20040221770A1 (en) 2004-11-11
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ES2545901T3 (en) 2015-09-16

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